DE2020595C3 - L-Aryl-3- (2-chlorallyl) thioureas, process for their preparation and their use as microbicides - Google Patents

Description

RR ¹

in which R is hydrogen, chlorine, bromine, trifluoromethyl, nitro or Ci-C ₄ ^{-AIlCyI and R 1 is} hydrogen, methyl or chlorine, as well as the bromine addition derivatives on the chlorallyl radical

2. l-Aryl-3- (2-chlorallyl) thioureas according to claim 1, in which the phenyl radical is substituted in the 3,4- or 3,5-position

3. l-Aryl-3- (2-chlorallyl) thioureas according to claim 1 of the general formula

S Cl

Il I

NH-C-NH-CH ₂ -C = CH ₂ 2:

in which two of the substituents R, R 'and R "are identical or different and Cl or CFj 3t mean, while the third stands for H.

4. 1- (3-Trifluoromethyl-4-chlorophenyl) -3- (2-chloroallyl) thiourea the formula

S Ci

Il I

NH-C-NH-CH ₂ -C = CH ₂

5. 1 - (3,5-Di-trifluoromethylphenyl) -3 - (. 2-chlorallyI) -thiourea the formula

S Cl

Il I

NH-C-NH-CH ₂ -C = CH ₂

6. 1 - (3,4-Dichlorophenyl) -3- (2-chloroallyl) -thioureas the formula

S Cl

NH-C-NH-CH ₂ -C = CH ₂

Cl

7,1- (3,5'-dichlorophenyl) -3- (2-chloroallyl) -thiourea the formula

S Cl

Il I

NH-C-NH-CH ₂ -C = CH ₂

8. Process for the preparation of thioureas according to claim I, characterized in that either an aryl isothionyanate of the general formula is used in a manner known per se Ar - N = C = S with 2-chloroallylamine of the formula

Cl
H ₂ N-CH ₃ -C = CH ₂

or an aniline of the general formula Ar-NH ₂ with 2-chlorohyl isothiocyanate of the formula

Cl
S = C = N-CH ₂ -C = CH ₂

reacts and optionally _{adds Cl 2} or Br _{2 to the} chlorallyl group

9. Microbiocidal agents containing at least one compound according to Claim 1.

The invention relates to biocide 1-aryl-3- (2-chloralyl) -thioureas the general formula

Cl

NH-C-NH-CH ₂ -C = CH ₂

which also includes the _{derivatives obtained by addition of Or or Br 2 to the} chloroallyl group, in which R is hydrogen, chlorine, bromine, trifluoromethyl, nitro or

4Γ, Ci-C ₄ -alkyl and R ^{1 are} hydrogen, methyl or chlorine.

It is preferred that no more than 3 of the substituents mentioned occur in the phenyl radical. Particularly effective representatives of formula I are in the 3,4- or 3,5-position des

4s phenyl nucleus substituted. The substituents are preferred electronegative (= electron attracting), but what the simultaneous presence of electroneutral len substituents such as methyl, ethyl, n-? ropyl, isopropyl, η-butyl or sec. Butyl does not exclude.

5 (i D ^! E active substances of the formula (I) are effective against human and plant pathogenic bacteria and fungi.

They are very effective against members of the Phycomycetes class, e.g. B. phytopathogenic fungi such as botrytis

5-j and Pricularia, but also against various others fungal pathogens in cereals, soy, maize, rice, vegetables, fruit growing and other crops.

They have a special effect against the following types of fungi; Cochliobolus miyabeanus species, Corticium-

6t) species, Cerospora ^ species, Alternaria species, Venturia inaequalis, Pödosphaera leucotricha, Ufomyces pha * seoii, Cercospora apii, Cercospora beticola, Cercospora musae, Piricularia sp., Erysiphe cichoriacearum, Penicil lium digitatum, Sphaerotheca humuli, Diplocarpon

6! I rosae, Uncinula necator, Coccomyces hiermalis, Cladosporium carpophilum, Erysiphe graminis hofdei, Monolinia (Sclerotinia) Laxa, Monolinia (Sclerotinia) fructicola, Piricularia oryzae, Puccinia recondita, P. Coronata,

P. glumamm, Puccinia graminis tritici, Aspergillus niger, Aspergillus terreus, Rhizoctonia, Fusarium, VerticilHum. This list does not claim to be complete.

The active ingredients or corresponding agents according to the invention also show a toxic effect in fungi that attack the plant in the soil and sometimes cause tracheomycoses, such as Fusarium cubense, Fusarium dianthi, Verticillium alboatrum and Phialophora cinerescens.

The active ingredients of formula (I) can also be used as bacteriostats, e.g. B. as soap additives, d. H, they can mainly be used in detergents and cleaning agents.

The compounds of the general formula are particularly suitable for this purpose

R'-

J /

R "

Cl

NH-C-NH-CH ₂ -C = CH ₂

(II)

proven, in which two of the substituents. ^ en R, R 'and R " are identical or different and are Cl or CFj, while the third is H.

The invention also relates to microbicidal agents which, as active component, contain at least one thiourea of the general formula (I) or one of the _{derivatives obtained by adding Cl 2} or Br _{2 to} the chloro group, in combination with one or more of the following additives: -, dispersants, wetting agents, adhesives, binders, thickeners or thinners, stabilizers or other active ingredients that influence animals and plants.

Another area of application for the active components is the textile sector. From aqueous dispersion and au.'i Solutions in organic solvents have an affinity in keratin fibers and can use them against the, 10 Protect against infestation by microorganisms.

The active ingredients of the formula (I) do not have any unpleasant odor and are good for healthy skin tolerated and have none / 15 compared to warm-blooded animals in the concentrations usual for disinfection toxic by-products.

These properties open up a very broad field of application for the compounds according to the invention. For example, they are used in cosmetics or in body care and hygiene in general as a disinfectant and preservative for a wide variety of technical and natural products. The application can be carried out in a wide variety of ways. As Applikationsmöglichkeiteri use in the form of> ^ suds, bubble baths, sprays, especially foam sprays, or solutions are mentioned, for example in organic solvents. With these applications the biocidal equipment is connected, which is mainly in the antibacterial and antifungal direction. _fl0

The focus is on the treatment of fiber materials, since it has been shown that the active ingredients of the formula (1) from an aqueous bath noun to be able to draw on a wide variety of fiber materials. It is thus possible to use these fiber materials by simply washing them with the active ingredients according to the invention containing washing and cleaning agents to be permanently biocidal, preferably antibacterial and antimycotic, and to protect against infestation Protect microorganisms and other pests.

Natural and synthetic fibers come into consideration as fiber materials. B. asbestos, but especially cellulosic fibers and especially cotton and nitrogen-containing fibers, such as leather and Wo ¹ Ie, should be mentioned. Both polycondensates such as polyadducts and polymers, that is to say polymers in the broader sense, and also glass fibers come into consideration as synthetic fiber materials. The polymer fibers can be derived from natural or synthetic polymers. Fibers of natural polymers are, for example, regenerated cellulose and cellulose dibis triacetate. Polyester, polyamide, polyurethane, polyacrylonitrile, polyvinyl chloride and polyethylene fibers, for example, are derived from synthetic polymers.

Agents which contain the active ingredients according to the invention can be in various forms, e.g. B. as bar, semi-solid and liquid soaps, as pastes, powders, emulsions, suspensions, solutions in organic solvents, as sprays, powders, granules, tablets, in capsules made of gelatine and others Material or as ointments.

The amounts in which the active ingredients of the formula (I) are used can be within a wide range vary. As a rule, however, 1 to 30 g per liter of liquor produce the desired effect Cleaning agents generally have an active ingredient content of 3 to 10 percent by weight, preferably but 0.5 to 3 percent by weight.

The new thioureas of the formula (I) can be prepared in a simple manner by a reactive derivative of thiocarbonic acid, e.g. B. thiophosgene, substituted with one according to formula (I) Aniline Ar-NHj and 2-chloroallylamine of the formula

Cl
I.
H ₂ N-CH ₂ -C = C

(III)

optionally implemented in the order.

You can z. B. react thiophosgene with the aniline and the resulting Arvlisothiocyanat Ar-N = C = S with 2-chlorallyiamine of the formula (III) for reaction bring.

In reverse order you can also use a reactive derivative of thiocarbonic acid Bring 2-chloroallylamine of the formula (III) to the reaction and the resulting isothiocyanate of the formula

Cl

= C = N-CH ₂ -C-CH ₂

(IV)

let react with the above aniline.

The isothiocyariate of the formula (IV) can be obtained more simply in a manner known per se by reacting 23-dichloropropene- (I) with an inorganic rhodailide, preferably alkali or ammonium rhodanide. Optionally, the Chiorallyigruppe can be before barren after coupling zlirfi Thiöhärnstöffderivat with CI2 or Br ₂ saturate.

example 1

S Cl

-C-NH-CH ₂ -C = CH ₂

(1)

185 parts of 4-chloro-3-trifluoromethylaniline in 200 parts by volume of acetonitrile are added to 134 parts of (2-chloro-allyl) mustard oil in 200 parts by volume of toluene and 0.1 part of triethylenediamine. After twenty hours of heating at 8O ⁰ C parts by volume is concentrated in vacuo to about 400, diluted with petroleum ether (50 to 70 ⁰ C), filtered and recrystallized from toluene-petroleum ether (40 to 70 ° C) recrystallized F.115bisll6 ° C [VerbindungNr. (l)].

In a similar manner, the following compounds of the formula (V) were obtained:

Cl

No. 22

\ -NH-C-NH-CH ₂ -C = CH ₂

(V)

Ver Ri R ₂ R ₃ R4 R ₅ F. am manure No. 2 H Cl Cl H H 81-83 C 3 H H H H H 93-95 C 4th H C ₂ H ₅ H H H 74-76 C 5 H CH ₃ H H H 86-87 C 6th H CF ₃ H H H 79-81 C 7th H CF ₃ H CF ₃ H 124-127 C 8th CH ₃ Cl H H H 107-108 C 9 Cl H NO ₂ H H 135-137 C 10 Br H CH ₃ H Br 140-141 C 11th H H Cl H H 97-98 C 12th H Cl H H H 101-103 C 13th H Cl CH ₃ H H 92-93 C 14th H NO ₂ CI H H 114-117 C 15th Cl H CI Cl H 125-126 C 16 Cl H II Cl H 115-116 C 17th H H C ₂ H ₅ H H 113-114 C 18th Cl Cl H H H 121-122 C 19th Cl H Cl H H 131-132 C 20th H Cl H CI H 124-125 C as well as the both connections No.! 21

S Cl

II. I

NH-C-NH-CH ₂ -CBr-CH ₂ Br F. 125 bisl26 ^o C (dec,)

NH-C-NH-CH ₂ -CBr-CH ₂ Br

CH ₃

F. 160 to 151 ⁰ C (decomp.)

Dust

Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. By Mixing with kaolin or talc can consist of dusts with preferably 1 to 6% active ingredient content getting produced.

Wettable powder

For the production of a Spritzp ^ .fers are for example the following components mixed and finely ground:

50 parts of active ingredient according to the present invention
20 parts of highly adsorptive silica
23 parts Bolus alba (kaolin)
3.5 parts of l-benzyI-2-stearyl-benzimidazole

Sodium 6,3-disulfate

3.5 parts of reaction product from p-tert-octylphenol and ethylene oxide

Emulsion concentrate

Easily soluble active ingredients can also be formulated as an emulsion concentrate according to the following instructions:

20 parts of active ingredient
70 parts of xylene
10 parts of a mixture

from a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate mixed. When diluting with water to the desired concentration, a sprayable one is produced Emulsion.

Application example 1

Zucchetti plants were grown in the greenhouse and once prophylactically with an aqueous one Spray liquor containing 0.1% of the active ingredient, sprayed. Two days later, the plants so treated became with spores of Erysiphe cichoriacearum DC. infected. After 12 to 14 days, those with the test spar> r <n « Compound no. (1) treated plants a fungal attack of 5% and those with compound no. (8) treated plants were not infested, while the untreated control plants were infested 100% was.

Application example 2

A mixture of equal parts of quartz sand and clay was mixed with an aqueous conidia suspension inoculated with Fusarium oxysporum, filled ir. pots and placed in a greenhouse cabin. After two Days the pots were sown with melons and then with an aqueous broth containing The equivalent of 30 kg / ha of active ingredient No. 2, evenly poured over.

The pots were kept adequately moist. After 14 days were in the treated test series

87% of the sown plants emerged healthy, compared to 6% in the untreated control vessels.

Application example 3

Bean plants were grown in the greenhouse and once prophylactically with an aqueous spray mixture, containing 0.1% of an active ingredient of the formula (I) sprayed. Two days after that, they were so treated Plants with uredospores of Uromyces phaseoli (Pers.) Wint. infected and for 2 days in a Spent humid chamber. After 10 to 14 days of subsequent incubation in the greenhouse, the the following active substances completely kill the fungus:

Connection no.

effect

9 100%

14 100%

15 100%

16 100%

17 100%

10 20th

25th

In an analogous experiment with grapevines as the active plant and Botrytis cinerea as the test mushroom Compounds No. 21 and 22 each showed a kill of 95%. Their effect was systematic.

In an analogous experiment with celery (Apium graveolens) as the active plant and Speloria apii as Compounds No. 3, 4 and 5 showed a death rate of 80, 80 and 95%.

Ahhduhg example 4

The active ingredients of the formula (I) show an extremely strong action against gram-positive bacteria especially against staphylococci and streptococci

The antibacterial activity in the dilution test was determined as follows:

15 BaKieriostasis and oaKteriziae

20 mg of active ingredient were dissolved in 10 ml of propylene glycol, 0.25 ml of which in 4.75 ml of sterile glucos <: - Broth added and then further diluted 1:10 in the tube. These solutions were then using inoculated with a bacterium and incubated for 48 hours at 37 ° C (bacteriostasis). After 24 hours Versuchs'lauer was streaked 1 loop from these cultures on glucose agar plates and for 24 hours 37 ° C incubated (bactericidal). After the times mentioned, the following limit concentrations in ppm the bacteriostasis or bactericides determined:

Bacterium Verb. Verb. Verb. Verb. Verb. Verb. Verb. Verb. Verb. Verb.

No. 2 No. 7 No. 6 No. 9 No. 11 No. 12 No. 13 No. 15 No. 16 No. 19 No. 20

Trich.menta- 2.5 2.5 30th 20th 20th 20th 10 20th 30th 30th 5 S. grophytes i E.coii 20th 20th 30th - 60 40 - 30th 30th - 20th 1 Asp.niger 60 - - - - - - - - - 60 ψ. Staph.aureus 2.5 0.3 5.5 3 20th 25th 10 2 20th 30th 0.6 I. - = Not checked. 1

Application example 5

Determination of

minimal inhibitory concentration (MIC) against
Bacteria and fungi in the gradient plate test

The compounds of the formula (I) were prepared in suitable formulations (e.g. as solutions in Dimethyl sulfoxide) of a certain concentration with warm Brain Heart Infusion Agar (bacteria) resp. Mycophil agar (mushrooms) mixed The liquid mixtures were poured onto a solidified, wedge-shaped base agar layer and also astonished calmly.

The test organisms were then applied in a line perpendicular to the gradient using a Pasteur pipette. After incubation for 24 hours at 37 ° C (bacteria) resp. 72 hours at 30 ⁰ C (fungi) was measured the length of the grown on the inoculation nuclei and expressed in ppm WirksSoff.

Verb. No. Minimum inhibitory concentration in ppm

Bacteriostasis

Staphylococcus
aureus

Fungistasis

Aspergillus
Niger

Trichophyton Trichophyton Epidermophyton Microsporum

mentagrophytes rubrum floccosum gypseum

0.4

0.8

5.5

20th

Comparative example

The bactericidal effect of the following compounds was determined:

I. Cl

S Cl

Il I

NH-C-NH-CH ₂ -C = CH ₂

according to Example I of the present application.

Cl

NH- C — NH- CH, - C = CH,

according to Example 1, compound Nf. 2 of the present Sign up.

Cl

NH-C-NH-CH ₂ -C = CH ₂

according to Example 1, compound no. 20 of the present application.

4. Cl

NH-CO-NH

CF ₃

5th Cl

IO

NH-CO -NH-

Cl

according to CH-PS 3 59 841.

method
(Agar incorporation test)

The test substance is dissolved in methyl cellosolve and a series of concentrations is produced by further dilution with methyl cellosolve. A corresponding amount of each concentration is mixed with the still liquid nutrient agar in a ratio of 1: 100. 15 ml each are poured into Petri dishes. After solidification the plates with 1 drop of a 24 hour old bacteria suspension of Salmonella pullorum VBIZ and Escherichia coli NCTC 8196 are inoculated and incubated for 48 hours at 37 ⁰ C. Then the lowest effective concentration of the tested concentration series (calculated on the nutrient agar) is determined.

The minimum inhibitory concentrations in ppm are compiled in the following table.

Tabel

Connection no.

Salmonella

pullorum

VBIZ

Escherichia
coli
NCTC 8196

10
6th

> 300
> 300

30th
1.3

30th

> 300
> 300

From the above results it is clear that the

Compounds 1 to 3 according to the invention are at least 10 times more active than the known

t / u: _j .. a ι c

JllgV.ll T UlIVl h>.

Claims (1)

Patent claims: 1. l-Aryl-3- (2-chlorallyl) -thioureas of the general formula S Cl Il I NH-C-NH-CH ₂ -C = CH ₂